Low-dimensional　organic-inorganic　hybrid　halides　(OIHs)　with　wide　emission　band　have　drawn　in　plenty　of　consideration　in　recent　years,　due　to　their　good　luminescence　potential,　low　cost　and　stable　chemical　properties.　In　this　work,　we　reported　two　new　zero-dimensional　(0D)　OIH　single-crystals,　(N-AEP)InCl6　⋅　H2O　(N-AEP=N-Aminoethylpiperazine,　1)　and　(N-AEP)InBr6　⋅　H2O　(2),　both　belong　to　the　orthorhombic　space　group　of　C2221.　Systematic　characterizations　of　the　compounds　including　crystal　structure,　thermal,　and　photophysical　properties　were　carried　out.　Luminescence　properties　studies　indicated　their　dual-emission　characteristics,　which　was　attributed　to　the　synergy　of　organic　and　inorganic　groups.　Significantly,　complex　1　showed　blue-light　(color　coordinates:　(0.18,　0.16))　emission　upon　UV　excitation,　while　a　rare　bluish-white　light　(color　coordinates:　(0.24,　0.24))　was　observed　in　2,　depending　on　the　assembly　of　high-energy　emission　in　(N-AEP)3+　and　low-energy　emission　in　[InBr6]3−　octahedron.　This　paper　offered　a　particular　example　on　the　research　for　In3+-based　single-component　materials　with　wide　emission　bands.　©　2022　Wiley-VCH　GmbH.